Semiconductor device and method of fabricating the same

ABSTRACT

A semiconductor device including a substrate; a bottom electrode on the substrate; a first dielectric layer on the bottom electrode, the first dielectric layer including a first metal oxide including at least one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb; a second dielectric layer on the first dielectric layer, the second dielectric layer including a second metal oxide including at least one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb, wherein the first metal oxide and the second metal oxide are different materials; a third dielectric layer on the second dielectric layer, the third dielectric layer including a metal carbon oxynitride; and an upper electrode on the third dielectric layer.

BACKGROUND

1. Field

Embodiments relate to a semiconductor device and a method of fabricatingthe same.

2. Description of the Related Art

Due to high degrees of integration and storage capability ofsemiconductor devices, a thin layer having high-k has recently been usedfor, e.g., a gate dielectric layer of a transistor, a dielectric layerof a capacitor, or a gate dielectric layer of a non-volatile memorydevice. By using such a high-k thin layer, a thin Equivalent OxideThickness (EOT) may be maintained and thus leakage current of the thinlayer may be greatly reduced.

SUMMARY

Embodiments are directed to a semiconductor device and a method offabricating the same, which represent advances over the related art.

It is a feature of an embodiment to provide a semiconductor device withimproved reliability.

At least one of the above and other features and advantages may berealized by providing a semiconductor device including a substrate; abottom electrode on the substrate; a first dielectric layer on thebottom electrode, the first dielectric layer including a first metaloxide including at least one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb; asecond dielectric layer on the first dielectric layer, the seconddielectric layer including a second metal oxide including at least oneof Hf, Al, Zr, La, Ba, Sr, Ti, and Pb, wherein the first metal oxide andthe second metal oxide are different materials; a third dielectric layerdisposed on the second dielectric layer, the third dielectric layerincluding a metal carbon oxynitride; and an upper electrode disposed onthe third dielectric layer.

The metal carbon oxynitride may be represented by Chemical Formula 1:

M_((1-x-y-z))O_(x)N_(y)C_(z)  (1),

in Chemical Formula 1, M may include at least one of Hf, Al, Zr, La, Ba,Sr, Ti, and Pb, x may be about 0.4 to about 0.8, and y and z may each beabout 0.05 or less.

A thickness of the first dielectric layer may be greater than athickness of the third dielectric layer.

The first dielectric layer may include zirconium oxide and the seconddielectric layer may include aluminum oxide.

The third dielectric layer may include zirconium carbon oxynitride.

A thickness of the first dielectric layer may be greater than athickness of the third dielectric layer.

A thickness of the first dielectric layer may be greater than athickness of the third dielectric layer.

At least one of the above and other features and advantages may also berealized by providing a method of fabricating a semiconductor device,the method including providing a substrate; forming a bottom electrodeon the substrate; forming a first dielectric layer on the bottomelectrode such that the first dielectric layer includes a first metaloxide including at least one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb;forming a second dielectric layer on the first dielectric layer suchthat the second dielectric layer includes a second metal oxide includingat least one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb and the first metaloxide and the second metal oxide include different materials; forming athird dielectric layer on the second dielectric layer such that thethird dielectric layer includes a metal carbon oxynitride; and formingan upper electrode on the third dielectric layer.

Forming the third dielectric layer may include providing a metalprecursor to the substrate including the second dielectric layer suchthat the metal precursor is adsorbed on the second dielectric layer,supplying a first purge gas to remove un-adsorbed metal precursor,supplying an oxidation gas, supplying a second purge gas to removeun-reacted oxidation gas, performing a plasma treatment whilenitridation gas is supplied, and supplying a third purge gas to removeun-reacted nitridation gas.

When providing the metal precursor, supplying the first purge gas,supplying the oxidation gas, supplying the second purge gas, performingthe plasma treatment while the nitridation gas is supplied are definedas a stacking layer process, and forming the third dielectric layer withthe metal carbon oxynitride layer includes repeating the stacking layerprocess multiple times, at least two stacking layer processes among themultiple times stacking layer processes may be performed with differentamount and pressure of the oxidation gas and with different amount andpressure of the nitridation gas.

The first dielectric layer may include zirconium oxynitride, the seconddielectric layer may include aluminum oxide, and the third dielectriclayer may include zirconium carbon oxynitride.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other features and advantages will become more apparent tothose of ordinary skill in the art by describing in detail exemplaryembodiments with reference to the attached drawings, in which:

FIG. 1 illustrates a sectional view of semiconductor device according toan embodiment;

FIGS. 2 through 4 illustrate sectional views of stages in a method offabricating a semiconductor device according to an embodiment;

FIG. 5 illustrates a timing diagram of a method of forming a thirddielectric layer in a method of fabricating a semiconductor deviceaccording to an embodiment;

FIG. 6 illustrates a timing diagram of a method of forming a thirddielectric layer in a method of fabricating a semiconductor deviceaccording to another embodiment;

FIGS. 7 and 8 illustrate sectional views of semiconductor devicesaccording to embodiments;

FIG. 9A through 10 illustrate graphs showing experimental results usingthe semiconductor devices of an embodiment; and

FIGS. 11 through 13 schematically illustrate examples of semiconductordevices fabricated according to an embodiment.

DETAILED DESCRIPTION

Korean Patent Application No. 10-209-0012501, filed on Feb. 16, 2009, inthe Korean Intellectual Property Office, and entitled: “SemiconductorDevice and Method of Fabricating the Same,” is incorporated by referenceherein in its entirety.

Example embodiments will now be described more fully hereinafter withreference to the accompanying drawings; however, they may be embodied indifferent forms and should not be construed as limited to theembodiments set forth herein. Rather, these embodiments are provided sothat this disclosure will be thorough and complete, and will fullyconvey the scope of the invention to those skilled in the art.

In the drawing figures, the dimensions of layers and regions may beexaggerated for clarity of illustration. It will also be understood thatwhen a layer or element is referred to as being “on” another layer orsubstrate, it can be directly on the other layer or substrate, orintervening layers may also be present. Further, it will be understoodthat when a layer is referred to as being “under” another layer, it canbe directly under, and one or more intervening layers may also bepresent. In addition, it will also be understood that when a layer isreferred to as being “between” two layers, it can be the only layerbetween the two layers, or one or more intervening layers may also bepresent. Like reference numerals refer to like elements throughout.

It will be understood that when an element is referred to as being“connected to” another element, it can be connected or coupled to theother element or intervening elements may be present, unless otherwiseexplicitly stated. As used herein, the term “and/or” includes any andall combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, etc. maybe used herein to describe various elements, components, and/orsections, these elements, components, and/or sections should not belimited by these terms. These terms are only used to distinguish oneelement, component or section from another element, component, orsection. Thus, a first element, component, or section discussed belowcould be termed a second element, component, or section withoutdeparting from the teachings of the present invention.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this invention belongs. It will befurther understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

In addition, when terms used in this specification are not specificallydefined, all the terms used in this specification (including technicaland scientific terms) can be understood by those skilled in the art.Further, when general terms defined in the dictionaries are notspecifically defined, the terms will have the normal meaning in the art.

Hereinafter, referring to FIG. 1, a semiconductor device according to anembodiment is described. FIG. 1 illustrates a sectional view of asemiconductor device according to an embodiment. Referring to FIG. 1, acapacitor 200 may be formed on a substrate 100.

The substrate 100 may include, e.g., a silicon substrate, a SOI (SiliconOn Insulator) substrate, a gallium arsenide substrate, a silicongermanium, a ceramic substrate, a quartz substrate, and/or a glasssubstrate for display. In addition, the substrate 100 may be, e.g., ap-type substrate, and although not illustrated in the drawings, asubstrate on which a p-type epitaxial layer is grown may be used.

Although not illustrated in the drawings, e.g., transistors, interlayerdielectric layers, contact holes, and metal interconnects, may be formedon the substrate 100.

The capacitor 200 may include, e.g., a bottom electrode 210, amulti-layer dielectric layer 240, and an upper electrode 250.

The bottom electrode 210, may include, e.g., TiN, TiAlN, TaN, W, WN, Ru,RuO₂, SrRuO₃, Ir, IrO₂, and/or Pt. Although not illustrated in thedrawings, the bottom electrode 210 may be connected to a conductiveregion, e.g., a source/drain region of a transistor formed on thesubstrate 100, through a contact hole.

The multi-layer dielectric layer 240 may be formed on the bottomelectrode 210. The multi-layer dielectric layer 240 may include, e.g., afirst dielectric layer 221, a second dielectric layer 225, and a thirddielectric layer 230.

The first and the second dielectric layers 221 and 225 may be stacked onthe bottom electrode 210. The first dielectric layer 221 may include afirst metal oxide including, e.g., Hf, Al, Zr, La, Ba, Sr, Ti, and/orPb. The second dielectric layer 225 may include a second metal oxideincluding, e.g., Hf, Al, Zr, La, Ba, Sr, Ti, and/or Pb. In animplementation, the first metal oxide of the first dielectric layer 221and the second metal oxide of the second dielectric layer 225 may bedifferent materials. The first dielectric layer 221 may be, e.g., azirconium oxide layer (ZrO₂), formed by oxidation of zirconium (Zr). Thesecond dielectric layer 225 may be, e.g., an aluminum oxide layer(Al₂O₃), formed by oxidation of aluminum (Al). Here, when the firstdielectric layer 221 is a zirconium oxide layer and the seconddielectric layer 225 is an aluminum oxide layer, a thickness of thezirconium oxide layer may be greater than a thickness of the aluminumoxide layer. In an implementation, the thickness of the first dielectriclayer 221 may be, e.g., about 30 Å to about 50 Å, and the thickness ofthe second dielectric layer 225 may be, e.g., about 3 Å to about 7 Å.

The third dielectric layer 230 may be, e.g., a metal carbon oxynitridelayer, formed on the second dielectric layer 225. The metal carbonoxynitride may be represented by Chemical Formula 1:

M_((1-x-y-z))O_(x)N_(y)C_(z)  (1).

In Chemical Formula 1, M may include, e.g., Hf, Al, Zr, La, Ba, Sr, Ti,and/or Pb. Further, in Chemical Formula 1, y and z may be about 0.05 orless and x may be about 0.4 to about 0.8. In an implementation, 1-x-y-zmay be about 0.2 to about 0.4. In other words, the metal carbonoxynitride may include carbon and nitrogen each in an amount of up toabout 5 mol %, based on the total moles of M, O, N, and C. Accordingly,a nitrogen and carbon content in the third dielectric layer 230 may berelatively small.

As a result, since the third dielectric layer 230 may include relativelysmall amount of carbon, permittivity may be improved and undesirableleakage current may be reduced. Also, since the third dielectric layer230 may include a relatively small amount of nitrogen, quality may beimproved and deterioration of the capacitor 200 may be avoided due to,e.g., deterioration of the bottom electrode 210 by an oxidation processto form the first and/or the second dielectric layers 221 and 225.Specifically, nitrogen contained in the third dielectric layer 230 maymove from an area adjacent to the upper electrode 250 to the bottomelectrode 210, and may deoxidize the bottom electrode 210 oxidizedduring the oxidation process used to form the first and/or the seconddielectric layers 221 and 225. Again, deterioration of capacitorcharacteristics may thereby be prevented. A more detailed description isincluded below referring to FIGS. 9A through 10.

In an implementation, the third dielectric layer 230 may be, e.g.,zirconium carbon oxynitride, Zr_((1-x-y-z))O_(x)N_(y)C_(z), formed byusing zirconium. The thickness of third dielectric layer 230 may be,e.g., about 10 Å to about 50 Å.

According to an embodiment, when the first, the second, and the thirddielectric layers 221, 225, and 230 include zirconium oxide, aluminumoxide, and zirconium carbon oxynitride, respectively, to improvepermittivity of the multi-layer dielectric layer 240 and electricalcharacteristics of the capacitor 200, the thickness of the firstdielectric layer 221 may be greater than the thickness of the thirddielectric layer 230. Since the third dielectric layer 230 may includenitrogen and carbon, it may have relatively inferior permittivity andlayer characteristics, compared to the first dielectric layer 221.

The upper electrode 250 may be formed on, and in contact with, the thirddielectric layer 230. In an implementation, the upper electrode 250 mayinclude, e.g., TiN, TiAlN, TaN, W, WN, Ru, RuO₂, SrRuO₃, Ir, IrO₂,and/or Pt. Although not illustrated in the drawings, the upper electrode250 may be connected to metal interconnects formed on the substrate 100through contact holes.

Therefore, a semiconductor device including the multi-layer dielectriclayer 240 formed in a stack structure with the first, the second, andthe third dielectric layers 221, 225, and 230 may not only avoiddeterioration of the capacitor 200 due to oxidation of the bottomelectrode 210, but may also improve reliability by reducing leakagecurrent.

Hereinafter, referring to FIGS. 1 through 6, a method of fabricating asemiconductor device according to an embodiment is described.

FIGS. 2 through 4 illustrate sectional views of stages in a method offabricating a semiconductor device according to an embodiment. FIG. 5illustrates a timing diagram of a method of forming the third dielectriclayer in a method of fabricating a semiconductor device according to anembodiment. FIG. 6 illustrates a timing diagram of a method of forming athird dielectric layer in a method of fabricating a semiconductor deviceaccording to another embodiment.

First, referring to FIG. 2, a bottom electrode 210 may be formed on asubstrate 100. The bottom electrode 210 may include, e.g., TiN, TiAlN,TaN, W, WN, Ru, RuO₂, SrRuO₃, Ir, IrO₂, and/or Pt.

Referring to FIG. 3, first and a second dielectric layers 221 and 225may be sequentially stacked on the bottom electrode 210. In animplementation, the first dielectric layer 221 may be formed as, e.g., azirconium oxide (ZrO₂) layer, and the second dielectric layer 225 may beformed as, e.g., an aluminum oxide (Al₂O₃) layer.

In particular, the semiconductor substrate 100 including the bottomelectrode 210 may be placed in a process chamber. Next, after setting apredetermined temperature and pressure, a zirconium precursor materialmay be supplied into the chamber. In an implementation, e.g., TEMAZ(Tetrakis Ethyl Methyl Amino Zirconium), TDMAZ (Tetrakis Di-Methyl AminoZirconium), TDEAZ (Tetrakis Di-Ethyl Amino Zirconium), Zr(OtBu)₄, and/orZrCl₄, may be used as the zirconium precursor material. Then, thezirconium precursor may be adsorbed on the bottom electrode 210.

Next, by supplying a purge gas, e.g., N₂, He, and/or Ar, into thechamber, remaining un-adsorbed zirconium precursor inside the chambermay be removed.

Then, an oxidation gas may be supplied into the chamber. The oxidationgas may include, e.g., O₂, O₃, H₂O, NO, NO₂, and/or N₂O. As theoxidation gas is supplied, plasma voltage may be applied inside thechamber to perform plasma treatment. When plasma is formed inside thechamber, the oxidation gas may become either plasma or remote-plasma,and a reaction of a layer to be formed may be accelerated and the layermay be more solidified. Thus, as the oxidation gas is supplied andplasma treatment is performed, the zirconium precursor adsorbed on thebottom electrode 210 may be oxidized to form a zirconium oxide layer.

Next, by supplying a purge gas, e.g., N₂, He, or Ar, into the chamber,remaining oxidation gas inside the chamber may be removed.

By repeating the steps above relating to the zirconium precursor apredetermined number of times, the first dielectric layer 221 includingthe zirconium oxide layer having a predetermined thickness on the bottomelectrode 210 may be formed.

Then, an aluminum precursor material may be supplied into the chamber.The aluminum precursor material may include, e.g., TMA (Tri MethylAluminum), DMAH (Di Methyl Aluminum Hydride), and/or DMAH-EPP (DiMethylAluminum Hydride Ethyl Piperidine). The aluminum precursor may beadsorbed on the first dielectric layer 221.

Next, after removing remaining un-adsorbed aluminum precursor inside thechamber by supplying a purge gas, e.g., N₂, He, and/or Ar, into thechamber, an oxidation gas may be supplied into the chamber and plasmatreatment may be performed to form an aluminum oxide layer. Then, bysupplying a purge gas, e.g., N₂, He, and/or Ar, into the chamber,remaining oxidation gas inside the chamber may be removed.

By repeating the steps above relating to the aluminum precursor apredetermined number of times, the second dielectric layer 225 includingthe aluminum oxide layer having a predetermined thickness may be formedon the first dielectric layer 221.

Referring to FIG. 4, a third dielectric layer 230 may be formed on thesecond dielectric layer 225. The third dielectric layer 230 may include,e.g., a metal carbon oxynitride layer. The metal carbon oxynitride maybe represented by Chemical Formula 1:

M_((1-x-y-z))O_(x)N_(y)C_(z)  (1).

In Chemical Formula 1, M may include, e.g., Hf, Al, Zr, La, Ba, Sr, Ti,and/or Pb. 1-x-y-z, x, y, and z, i.e., the metal, oxygen, nitrogen, andcarbon content of the metal carbon oxynitride may be the same asdescribed above. In other words, the metal carbon oxynitride may includecarbon and nitrogen each in an amount of up to about 5 mol %, based onthe total moles of M, O, N, and C. Referring to FIGS. 4 and 5, formingthe third dielectric layer 230 on the second dielectric layer 225 isdescribed in more detail.

After forming the second dielectric layer 225, a metal precursormaterial may be supplied to the chamber. Here, the metal precursormaterial may include, e.g., Hf, Al, Zr, La, Ba, Sr, Ti, and/or Pb. Whenthe third dielectric layer 230 is a zirconium carbon oxynitride layer,e.g., TEMAZ, TDMAZ, TDEAZ, Zr(OtBu)₄, and/or ZrCl₄, may be used as themetal precursor material. When the third dielectric layer 230 is analuminum carbon oxynitride layer, e.g., TMA, DMAH, and/or DMAH-EPP, maybe used as the metal precursor material. The metal precursor may beadsorbed on the second dielectric layer 225.

Next, by supplying a purge gas, e.g., N₂, He, and/or Ar, into thechamber, remaining un-adsorbed metal precursor inside the chamber may beremoved.

Then, an oxidation gas may be supplied to the chamber. The oxidation gasmay include, e.g., O₂, O₃, H₂O, NO, NO₂, and/or N₂O. Thus, the metalprecursor adsorbed on the second dielectric layer 225 may be oxidized.

Next, by supplying a purge gas, e.g., N₂, He, and/or Ar, into thechamber, remaining un-reacted oxidation gas inside the chamber may beremoved.

Then, a nitridation gas may be supplied to the chamber. The nitridationgas may include, e.g., N₂, NH₃, NO, and/or N₂O. As the nitridation gasis supplied, plasma voltage may be applied inside the chamber to performa plasma treatment. That is, when nitridation gas is supplied and plasmatreatment is performed, the metal precursor that was oxidized in theprevious step may be nitrided to form the metal carbon oxynitride layer.

Next, by supplying a purge gas, e.g., N₂, He, and/or Ar, into thechamber, remaining un-reacted nitridation gas inside the chamber may beremoved.

By repeating the steps above relating to the metal precursor apredetermined number of times, the third dielectric layer 230, which maybe a metal carbon oxynitride layer, may be stacked on the seconddielectric layer 225. In an implementation, by adjusting a number ofrepetitions, a thickness of third dielectric layer 230 may becontrolled.

Therefore, in the method of fabricating the semiconductor deviceaccording to an embodiment, the third dielectric layer 230, asillustrated in FIG. 5, may be formed by the process sequence of: metalprecursor supply→purge→oxidation gas supply→purge→nitridation gas supplyand plasma treatment→purge. If the metal carbon oxynitride formed usingthe process sequence above is represented by Chemical Formula 1:

M_((1-x-y-z))O_(x)N_(y)C_(z)  (1),

x may be about 0.4 to about 0.8, and y and z may each be about 0.05 orless, thus the content of nitrogen and carbon in the third dielectriclayer 230 may be relatively small. In other words, nitrogen and carbonmay each be included in the metal carbon oxynitride in an amount of upto about 5 mol %, based on the total moles of M, O, N, and C. In animplementation, 1-x-y-z may be about 0.2 to about 0.4.

Specifically, in the method of fabricating the semiconductor deviceaccording to the present embodiment, the content of nitrogen and carbonmay be relatively small compared to other processes, e.g., firstsupplying a nitridation gas and then supplying oxidation gas afterplasma treatment. Thus, since the oxidation gas may be suppliedrelatively early, carbon and nitrogen in the metal precursor may beconsumed by the oxidation gas and thus the carbon and nitrogen contentof the metal carbon oxynitride may be small. Also, since reactive sitesof the precursor may be first bonded with oxygen, a relatively smallnumber of reactive sites may remain when the nitridation gas issupplied. As a result, in the metal carbon oxynitride layer, nitrogencontent may be relatively small.

As a result, since the third dielectric layer 230 according to anembodiment may include a relatively small amount of carbon, permittivitymay be improved and leakage current may be reduced. Also, since thethird dielectric layer 230 may include a relatively small amount ofnitrogen, layer quality may be improved and deterioration of thecapacitor 200 due to deterioration of the bottom electrode 210 duringthe oxidation process to form the first and/or the second dielectriclayer 221 and 225 may be prevented. ALD (Atomic Layer Deposition) orPEALD (Plasma Enhanced ALD) may be used to form the first, the second,and the third dielectric layers 221, 225, and 230. Also, the first, thesecond, and the third dielectric layers 221, 225, and 230 may be formedin-situ in the same chamber.

Next, again referring to FIG. 1, the capacitor 200 may be completed byforming an upper electrode 250 on the third dielectric layer 230. Theupper electrode 250, may include, e.g., TiN, TiAlN, TaN, W, WN, Ru,RuO₂, SrRuO₃, Ir, IrO₂, and/or Pt.

As described above, FIG. 6 illustrates a timing diagram of a method offorming the third dielectric layer in a method of fabricating asemiconductor device according to another embodiment.

Referring to FIGS. 1 through 6, the method of fabricating thesemiconductor device according to the present embodiment may beidentical to the previous embodiment, except that when forming the metalcarbon oxynitride of the third dielectric layer 230, the presentembodiment may not apply identical conditions to all cycles to formmetal carbon oxynitride. Thus, in the present embodiment, the metalcarbon oxynitride of third dielectric layer 230 may be formed bymultiple stacking layer processes. Further, during the multiple stackinglayer processes at least two processes may be performed with differentamounts and pressures of oxidation gas and nitridation gas.

Specifically, as illustrated in FIG. 6, in the present embodiment, wheneach atomic layer is formed by performing one cycle, i.e., one stackinglayer process, which includes a process sequence of, e.g., metalprecursor supply→a first purge→oxidation gas supply→a secondpurge→nitridation gas supply and plasma treatment→a third purge, eachcycle may be performed with different type, quantity, and/or pressure ofoxidation gas and nitridation gas. As a result, the metal carbonoxynitride formed during each cycle, which may be represented byChemical Formula 1, may have different contents of oxygen, nitrogen, andcarbon. Such metal carbon oxynitride layers may have atomic layers wherethe contents of oxygen, carbon, and nitrogen in each atomic layer aredifferent in each atomic layer. As a result, although crystal growth mayoccur in one of the atomic layers, adjacent layers may prevent thecrystal growth and formation of large crystals may be avoided.Therefore, in the third dielectric layer 230, formation of a leakagecurrent path may be prevented.

Among the multiple layer stacking process cycles, at least two cyclesmay be performed using different types, quantity, and pressure of theoxidation gas and nitridation gas. Thus, the third dielectric layer 230may be formed with different process conditions for all cycles, or byperforming different group processes consisting of multiple cyclesrepeatedly.

As described above, a capacitor included in the semiconductor deviceaccording to an embodiment may include various capacitors that may beused in semiconductor devices, e.g., a flat-type capacitor and acylinder-type capacitor. Hereinafter, by referring to FIGS. 7 and 8, asemiconductor device according to an embodiment is described.

FIG. 7 illustrates a semiconductor device including a flat-typecapacitor according to an embodiment.

Referring to FIG. 7, a device isolation layer 102 may be formed in asubstrate 100 to isolate an active region and a field region. Gateelectrodes 110 may be disposed on the substrate 100. Also, asource/drain region 111, which may be aligned with the gate electrode110, may be disposed in the substrate 100. A first interlayer dielectriclayer 120 may be formed on the substrate 100 and the gate electrodes110.

A first contact 122 may be formed in the first interlayer dielectriclayer 120 on the source/drain region 111. The first contact 122 mayelectrically connect the source/drain region 111 in the substrate 100 toa bottom electrode 210 a of a flat-type capacitor 200 a. Also, a bitline contact (not illustrated), which may be electrically connected toanother source/drain region 111 of the substrate 100, may be formed inthe first interlayer dielectric layer 120.

A second interlayer dielectric layer 130 may be formed on the firstinterlayer dielectric layer 120. The flat-type capacitor 200 a, whichmay be electrically connected to the first contact 122, may be formed inthe second interlayer dielectric layer 130.

The flat-type capacitor 200 a may include the bottom electrode 210 aformed on the first contact 122, a multi-layer dielectric layer 240 a,and an upper electrode 250 a. The upper electrode 250 a may be connectedto a wire contact 152, which may connect a wire 162 to the upperelectrode 250 a. Here, the flat-type capacitor 200 a may include themulti-layer dielectric layer 240 a according to the previously describedembodiment.

FIG. 8 illustrates a semiconductor device including a cylinder-typecapacitor according to an embodiment.

Referring to FIG. 8, a device isolation layer 102 may be formed in asubstrate 100 to isolate an active region and a field region. Gateelectrodes 110 may be disposed on the substrate 100. Also, asource/drain region 111 aligned with the gate electrode 110 may beformed in the substrate 100.

A first interlayer dielectric layer 120 may be formed on the substrate100 and the gate electrodes 110. A first contact 124, which mayelectrically connect the source/drain region 111 to a bottom electrode210 b of a cylinder-type capacitor 200 b may be formed in the firstinterlayer dielectric layer 120. Also, a first bit line contact 125,which may be electrically connected to another source/drain region 111of the substrate 100, may be formed in the first interlayer dielectriclayer 120.

An etch stop layer 131 may be formed on the first interlayer dielectriclayer 120. A second interlayer dielectric layer 130 may be formed on theetch stop layer 131. A second bit line contact 152 connected to a bitline 162 may be formed in the second interlayer dielectric layer 130 onthe first bit line contact 125.

The cylinder-type capacitor 200 b may be formed on the first contact124. The cylinder-type capacitor 200 b may include the bottom electrode210 b, a multi-layer dielectric layer 240 b, and an upper electrode 250b. The upper electrode 250 b may be connected to a wire contact 154,which may connect a wire 164 to the upper electrode 250 b. Here, thecylinder-type capacitor 200 b may include the multi-layer dielectriclayer 240 b according to an embodiment.

More detailed descriptions of the embodiments are explained by using thefollowing specific experimental examples, and explanation for thecontent not described here is skipped since it is obvious for thoseskilled in the art.

Experimental Example 1

As described below, experiments were conducted on first and secondexamples and a first comparison example. For each of the first andsecond example and the first comparison example, the bottom electrodeand the upper electrode were identically formed with TiN, while themulti-layer dielectric layer was formed differently.

In the first example the multi-layer dielectric layer was formed bysequentially stacking a zirconium oxide layer, an aluminum oxide layer,and a zirconium carbon oxynitride layer on the bottom electrode.Specifically, the zirconium oxide layer was formed by repeating 42times, a process cycle, which included: metal precursor (TEMAZ)supply→purge (Ar)→oxidation gas (O₂) supply and plasma treatment→purge(Ar). The aluminum oxide layer was formed by repeating 3 times, aprocess cycle, which included: metal precursor (TMA) supply→purge(Ar)→oxidation gas (O₂) supply and plasma treatment→purge (Ar). Thezirconium carbon oxynitride layer was formed by repeating 22 times, aprocess cycle, which included metal precursor (TEMAZ) supply→purge(Ar)→oxidation gas (O2) supply→purge (Ar)→nitridation gas (NH₃) supplyand plasma treatment→purge (Ar). As a result, the EOT of the multi-layerdielectric layer was 9.8 Å.

In the second example, similar to the first example, a multi-layerdielectric layer was formed by sequentially stacking a zirconium oxidelayer, an aluminum oxide layer, and a zirconium carbon oxynitride layeron the bottom electrode, except the number of repetitions of processcycles to form the zirconium carbon oxynitride layer were different.Specifically, in the second example, the zirconium carbon oxynitridelayer was formed by repeating the process cycle used to form thezirconium carbon oxynitride in the first experimental example 30 times.As a result, the EOT of the multi-layer dielectric layer was 10.4 Å.

In the first comparison example, the multi-layer dielectric layer wasformed by sequentially stacking a first zirconium oxide layer, analuminum oxide layer, and a second zirconium oxide layer on the bottomelectrode. Specifically, the first zirconium oxide layer and thealuminum oxide layer were stacked sequentially on the bottom electrodeby using the identical method used in the first example. The secondzirconium oxide layer was formed on the aluminum oxide layer the byrepeating 14 times the process cycle used to form the zirconium oxidelayer in the first example. As a result, the EOT of multi-layerdielectric layer was 10.4 Å.

Next, while applying various voltages to the bottom electrodes and theupper electrodes, leakage current and capacitance were measured in thefirst and the second examples and the first comparison example. Theresults are illustrated in FIGS. 9A and 9B. Referring to FIG. 9A, thex-axis represents the voltage applied to each end of the bottomelectrode and the upper electrode and the y-axis represents leakagecurrent density with the unit of A/cm². Referring to FIG. 9B, the x-axisrepresents the voltage applied to each end of the bottom electrode andthe upper electrode, and the y-axis represents the capacitancenormalized by an applied voltage of 0 V.

First, referring to FIG. 9A, the first and the second examples exhibitedimprovement in leakage current characteristics compared to the firstcomparison example. Specifically, in the first and the second examplesand the first comparison example, when the leakage current was 100nA/cm², the voltages applied to each end of the bottom electrode and theupper electrode are summarized in Table 1.

TABLE 1 First Comparison First Example Second Example Example −1.0 V/0.7V −1.3 V/1.0 V −1.3 V/0.7 V

Referring to Table 1 above, in the second example having the same EOT(10.4 Å) as the first comparison example, since a leakage current of 100nA/cm² occurred at higher voltage, it may be seen that electricalcharacteristics of the capacitor according to the second example wereimproved.

Next, referring to FIG. 9B, in the first and the second examples it maybe seen that the capacitance remained relatively constant compared tothe first comparison example. Specifically, in the first and the secondexamples and the first comparison example, a ratio of capacitance wherea voltage of 0.6 V was applied to the bottom electrode and the upperelectrode to capacitance where a voltage of −0.6 V was applied to thebottom electrode and the upper electrode is summarized in Table 2.

TABLE 2 First Comparison First Example Second Example Example 96.4%97.1% 91.3%

Referring to Table 2 above, since the first and second examples, wherethe zirconium carbon oxynitride was formed under the upper electrode,exhibited relatively constant capacitance, compared to the firstcomparison example where the zirconium oxide layer was formed under theupper electrode, it may be seen that electrical characteristics ofcapacitance were improved.

Experimental Example 2

Experiments were conducted on the first and the second examples and thefirst comparison example, as well as second and third comparisonexamples. Here, in the second and third comparison examples, the bottomand the upper electrodes were formed with TiN, identical to the previousexamples, with only the multi-layer dielectric layers formeddifferently.

In the second comparison example, the multi-layer dielectric layer wasformed by stacking a zirconium carbon oxynitride layer, an aluminumoxide layer, and a zirconium oxide layer on the bottom electrode.Specifically, the zirconium carbon oxynitride layer was formed byrepeating 22 times the cycle used to form the zirconium carbonoxynitride layer in the first example. The aluminum oxide layer wasformed by repeating 3 times the cycle used to form the aluminum oxidelayer in the first example. The zirconium oxide layer was formed byrepeating 42 times the cycle used to form the zirconium oxide layer inthe first example. The resulting EOT of the multi-layer dielectric layerwas 11.9 Å.

In the third comparison example, after forming the identical multi-layerdielectric layer formed in the first comparison example, plasmatreatment was performed for 1 minute while supplying NH₃ gas. Thus, themulti-layer dielectric layer in the first example was nitrified. Theresulting EOT of the multi-layer dielectric layer was 10.3 Å.

Next, while applying various voltages to the bottom electrode and theupper electrode, capacitance of the first and second examples and thefirst through third comparison examples were measured. Here, the resultsof the first through third comparison examples are illustrated in FIG.10. In FIG. 10, the x-axis represents voltage applied to each end of thebottom electrode and the upper electrode and the y-axis represents thecapacitance normalized by an applied voltage of 0 V.

Referring to FIGS. 9B and 10, in the first and second examples it may beseen that the capacitance remained relatively constant compared to thefirst through third comparison examples. Specifically, in the first andsecond examples and the first through the third comparison examples, aratio of capacitance where a voltage of 0.6 V is applied to capacitancewhere a voltage of −0.6 V is applied to the bottom electrode and theupper electrode is summarized in Table 3.

TABLE 3 First Second Third First Second Comparison Comparison ComparisonExample Example Example Example Example 96.4% 97.1% 91.3% 93.0% 93.1%

Referring to Table 3, in the first and second examples that included thezirconium oxide layer, the aluminum oxide layer, and the zirconiumcarbon oxynitride layer in the multi-layer dielectric layer, it may beseen that capacitance remained relatively constant, compared to thesecond comparison example that included the zirconium carbon oxynitridelayer, the aluminum oxide layer, and the zirconium oxide layer in themulti-layer dielectric layer. Also, in the second example it may be seenthat capacitance remained relatively constant, compared to the thirdcomparison example that formed the multi-layer dielectric layer followedby nitrification. Thus, in the first and the second examples it may beseen that capacitance remained relatively constant, compared to thefirst comparison example including the dielectric layer without nitrogencomponent, the second comparison example including the dielectric layercontaining nitrogen component and different stack order, and the thirdcomparison example that formed the multi-layer dielectric layer followedby nitrification. As a result, in the first and second examples, it maybe seen that electrical characteristics of capacitance were improvedcompared to the first through third comparison examples.

In the descriptions above, although it was illustrated that themulti-layer dielectric layer was placed between the bottom electrode andthe upper electrode and used as capacitor, it is not limited thereto.For example, in another implementation the multi-layer dielectric layermay be used as an interlayer dielectric layer, e.g., a gate dielectriclayer, tunnel dielectric layer, or block dielectric layer, of a flashmemory device, which may be part of each memory cell. Specifically, inanother implementation when the multi-layer dielectric layer formed withstack structure of the first through third dielectric layers is used ina semiconductor device, e.g., flash memory device, deterioration ofsemiconductor devices due to oxidation of a floating gate may beprevented, and reliability may be improved due to reduction of leakagecurrent.

FIGS. 11 through 13 illustrate block diagrams of examples ofsemiconductor devices fabricated according to embodiments.

Referring to FIG. 11, a system according to an embodiment may include amemory 510 and a memory controller 520 connected to the memory 510.Here, DRAM (Dynamic Random Access Memory) and flash memory fabricatedaccording to the previously described embodiments may be used for thememory 510.

The memory controller 520 may provide the memory 510 with input signalsthat may control operations of the memory 510, e.g., command signals andaddress signals to control read operations and write operations. In thelogic circuit of the memory controller 520, capacitors formed accordingto an embodiment or transistors that include the multi-layer dielectriclayer as gate dielectric layer formed according to an embodiment may beused.

The system, may be used in, e.g., electronic devices such as cell phone,two-way communication system, one way pager, two-way pager, personalcommunication system, portable computer, PDA (Personal DigitalAssistant), audio and/or video player, digital and/or video camera,navigation system, and GPS (Global Positioning System).

Referring to FIG. 12, a system according to another embodiment mayinclude a memory 510, a memory controller 520, and a host system 530.Here, the host system 530 may be connected to the memory controller 520through a bus and may provide the memory controller 520 with controlsignals to enable the memory controller 520 to control operations of thememory 510. Such host system 530 may be, e.g., a processing system usedin cell phone, two-way communication system, one way pager, two-waypager, personal communication system, portable computer, PDA (PersonalDigital Assistant), audio and/or video player, digital and/or videocamera, navigation system, and GPS (Global Positioning System).

Although FIG. 12 shows the memory controller 520 in between the memory510 and the host system 530, it is not limited thereto. In animplementation, the memory controller 520 may be selectively omitted ina system.

Referring to FIG. 13, a system according to another embodiment may be,e.g., a computer system 560 that includes a CPU (Central ProcessingUnit) 540 and a memory 510. In the computer system 560, the memory 510may be connected to the CPU 540 directly or through typical computer busarchitecture and may be DRAM or non-volatile memory. Such memories maybe used to store OS (Operation System) instruction set, BIOS (BasicInput/Output Start up) instruction set, and ACPI (Advanced Configurationand Power Interface) instruction set, or can be used as mass storagedevice such as SSD (Solid State Disk). Also, in the logic circuit of theCPU 540 capacitors formed according to an embodiment or transistors thatuse the multi-layer dielectric layer as gate dielectric layer formedaccording to an embodiment may be used. Although in FIG. 13 all thecomponents included in the computer system 560 are not illustrated, itis not limited thereto. Also, although in FIG. 11 the memory controller520 is omitted between the memory 510 and the CPU 540, the memorycontroller 520 may be placed between the memory 510 and the CPU 540 inanother embodiment.

By using a high-k material, a metal oxide layer can be used as acapacitor dielectric layer. During a fabrication process of the metaloxide layer as a dielectric layer according to an embodiment, a bottomelectrode may not be oxidized. Accordingly, electrical characteristicsof the capacitor may not be deteriorated.

Exemplary embodiments have been disclosed herein, and although specificterms are employed, they are used and are to be interpreted in a genericand descriptive sense only and not for purpose of limitation.Accordingly, it will be understood by those of ordinary skill in the artthat various changes in form and details may be made without departingfrom the spirit and scope of the present invention as set forth in thefollowing claims.

1. A semiconductor device, comprising: a substrate; a bottom electrodeon the substrate; a first dielectric layer on the bottom electrode, thefirst dielectric layer including a first metal oxide including at leastone of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb; a second dielectric layer onthe first dielectric layer, the second dielectric layer including asecond metal oxide including at least one of Hf, Al, Zr, La, Ba, Sr, Ti,and Pb, wherein the first metal oxide and the second metal oxide aredifferent materials; a third dielectric layer disposed on the seconddielectric layer, the third dielectric layer including a metal carbonoxynitride; and an upper electrode disposed on the third dielectriclayer.
 2. The semiconductor device as claimed in claim 1, wherein themetal carbon oxynitride is represented by Chemical Formula 1:M_((1-x-y-z))O_(x)N_(y)C_(z)  (1), in Chemical Formula 1, M includes atleast one of Hf, Al, Zr, La, Ba, Sr, Ti, and Pb, x is about 0.4 to about0.8, and y and z are each about 0.05 or less.
 3. The semiconductordevice as claimed in claim 2, wherein a thickness of the firstdielectric layer is greater than a thickness of the third dielectriclayer.
 4. The semiconductor device as claimed in claim 1, wherein thefirst dielectric layer includes zirconium oxide and the seconddielectric layer includes aluminum oxide.
 5. The semiconductor device asclaimed in claim 4, wherein the third dielectric layer includeszirconium carbon oxynitride.
 6. The semiconductor device as claimed inclaim 4, wherein a thickness of the first dielectric layer is greaterthan a thickness of the third dielectric layer.
 7. The semiconductordevice as claimed in claim 1, wherein a thickness of the firstdielectric layer is greater than a thickness of the third dielectriclayer. 8-11. (canceled)